Denis Law and Dave Mackay appear as part of the 11-piece set, designed to celebrate 150 years of the English FA and 140 years of the SFA.
Eleven players from the four home nations will feature on individual stamps, including former Northern Ireland international and Man United star George Best, and ex-England winger and Celtic manager, John Barnes.
The players all appear in the strip of their national side and, when placed together, form a traditional team photograph.
Denis Law said: "As a schoolboy playing football I never dreamed I would appear on a stamp.
"I am extremely honoured."
FA General Secretary, Alex Horne, said: "The Royal Mail has done a fantastic job, and the artwork by Andrew Kinsman is particularly striking."
Fans wishing to get their hands on the full set of stamps, costing £6.60, can do so from today by going to their local post office, or by visiting www. royalmail.com/footballheroes